Well defined copper(I) catalysts for the chemoselective oxidation reaction of alcohols to aldehydes

Detalhes bibliográficos
Autor(a) principal: Machado, Beatriz Pereira
Data de Publicação: 2023
Tipo de documento: Dissertação
Idioma: eng
Título da fonte: Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
Texto Completo: http://hdl.handle.net/10362/162946
Resumo: One of the key concerns in contemporary chemistry is the development of sustainable processes that adhere as closely as possible to the principles of Green Chemistry without com- promising the activity of involved processes. Several principles can be applied in the develop- ment of this work, including the catalysis and the atomic economy, among others. The harsh conditions and the disposal of subproducts that characterize typical oxidation reactions pose significant challenges for the chemoselective oxidation of alcohols to benzaldehydes. To tackle these issues, the use of copper(I) complexes comprising diimine ligands, usually bipyridine and phenanthroline shown promising outcomes. Furthermore, new studies by our research group, suggests that bis-aryldiiminoacenaphthene ligands may also be effective, and even in- crease catalyst activity of such systems. However, such complexes regularly incorporate halo- gens as counterions. The impact of the diimine backbone on the catalytic activity and stability was investigated in the newly synthesised compounds. Additionally, the effects of the coun- terion and chelating solvent on the activity and stability were examined. Characterization of all compounds included mono and heteronuclear 1D and 2D-NMR, IR, EA, UV/Vis, and, when possible, X-ray diffraction. The efficiency of all compounds was tested in the oxidation reaction, and they all revealed to be active. Various conditions of the catalytic system were studied to optimize it, and subsequently, the catalytic system was tested with benzyl, allylic, and aliphatic alcohols for efficiency.
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spelling Well defined copper(I) catalysts for the chemoselective oxidation reaction of alcohols to aldehydesDABDADBIANcopper(I)benzylic alcoholallylic alcoholDomínio/Área Científica::Engenharia e Tecnologia::Engenharia QuímicaOne of the key concerns in contemporary chemistry is the development of sustainable processes that adhere as closely as possible to the principles of Green Chemistry without com- promising the activity of involved processes. Several principles can be applied in the develop- ment of this work, including the catalysis and the atomic economy, among others. The harsh conditions and the disposal of subproducts that characterize typical oxidation reactions pose significant challenges for the chemoselective oxidation of alcohols to benzaldehydes. To tackle these issues, the use of copper(I) complexes comprising diimine ligands, usually bipyridine and phenanthroline shown promising outcomes. Furthermore, new studies by our research group, suggests that bis-aryldiiminoacenaphthene ligands may also be effective, and even in- crease catalyst activity of such systems. However, such complexes regularly incorporate halo- gens as counterions. The impact of the diimine backbone on the catalytic activity and stability was investigated in the newly synthesised compounds. Additionally, the effects of the coun- terion and chelating solvent on the activity and stability were examined. Characterization of all compounds included mono and heteronuclear 1D and 2D-NMR, IR, EA, UV/Vis, and, when possible, X-ray diffraction. The efficiency of all compounds was tested in the oxidation reaction, and they all revealed to be active. Various conditions of the catalytic system were studied to optimize it, and subsequently, the catalytic system was tested with benzyl, allylic, and aliphatic alcohols for efficiency.Uma das principais preocupações da química contemporânea é o desenvolvimento de processos sustentáveis que se aproximem o mais possível dos princípios da Química Verde sem comprometer a atividade em processos envolvidos. Diversos princípios podem ser apli- cados no decorrer deste trabalho, nomeadamente a catálise e economia atómica, entre outros. As condições adversas e a eliminação dos subprodutos que caracterizam reações de oxidação representam desafios significativos para a oxidação quimioselectiva de álcoois a aldeídos. Para resolver estas questões, foram utilizados complexos de cobre(I) que incluem ligandos diimina, geralmente bipiridina e fenantrolina. Além disso, novos estudos do nosso grupo de investiga- ção sugerem que os ligandos bis-arildiiminoacenafteno também podem ser eficazes e até au- mentar a atividade catalítica deste tipo de sistemas. No entanto, esses complexos incorporam regularmente halogéneos como contra-iões. O impacto da estrutura da diimina na atividade e estabilidade do complexo foi investigado nos compostos recentemente sintetizados. Adicio- nalmente, foram examinados os efeitos do contra-ião e do solvente quelante na atividade e estabilidade do catalisador. A caracterização de todos os compostos incluiu 1D e 2D-RMN mono e heteronuclear, IV, AE, UV/Vis e, quando possível, difração de raios-X. A eficiência de todos os compostos foi testada na reação de oxidação, e todos eles se relaram ser ativos. Foram estudadas várias condições do sistema catalítico para o otimizar e, subsequentemente, este foi testado com álcoois benzílicos, alílicos e alifáticos para verificar a sua eficiência.Rosa, VitorLima, JoãoRUNMachado, Beatriz Pereira2024-01-31T12:25:58Z2023-112023-11-01T00:00:00Zinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisapplication/pdfhttp://hdl.handle.net/10362/162946enginfo:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2024-03-11T05:45:59Zoai:run.unl.pt:10362/162946Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-20T03:59:10.285332Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse
dc.title.none.fl_str_mv Well defined copper(I) catalysts for the chemoselective oxidation reaction of alcohols to aldehydes
title Well defined copper(I) catalysts for the chemoselective oxidation reaction of alcohols to aldehydes
spellingShingle Well defined copper(I) catalysts for the chemoselective oxidation reaction of alcohols to aldehydes
Machado, Beatriz Pereira
DAB
DAD
BIAN
copper(I)
benzylic alcohol
allylic alcohol
Domínio/Área Científica::Engenharia e Tecnologia::Engenharia Química
title_short Well defined copper(I) catalysts for the chemoselective oxidation reaction of alcohols to aldehydes
title_full Well defined copper(I) catalysts for the chemoselective oxidation reaction of alcohols to aldehydes
title_fullStr Well defined copper(I) catalysts for the chemoselective oxidation reaction of alcohols to aldehydes
title_full_unstemmed Well defined copper(I) catalysts for the chemoselective oxidation reaction of alcohols to aldehydes
title_sort Well defined copper(I) catalysts for the chemoselective oxidation reaction of alcohols to aldehydes
author Machado, Beatriz Pereira
author_facet Machado, Beatriz Pereira
author_role author
dc.contributor.none.fl_str_mv Rosa, Vitor
Lima, João
RUN
dc.contributor.author.fl_str_mv Machado, Beatriz Pereira
dc.subject.por.fl_str_mv DAB
DAD
BIAN
copper(I)
benzylic alcohol
allylic alcohol
Domínio/Área Científica::Engenharia e Tecnologia::Engenharia Química
topic DAB
DAD
BIAN
copper(I)
benzylic alcohol
allylic alcohol
Domínio/Área Científica::Engenharia e Tecnologia::Engenharia Química
description One of the key concerns in contemporary chemistry is the development of sustainable processes that adhere as closely as possible to the principles of Green Chemistry without com- promising the activity of involved processes. Several principles can be applied in the develop- ment of this work, including the catalysis and the atomic economy, among others. The harsh conditions and the disposal of subproducts that characterize typical oxidation reactions pose significant challenges for the chemoselective oxidation of alcohols to benzaldehydes. To tackle these issues, the use of copper(I) complexes comprising diimine ligands, usually bipyridine and phenanthroline shown promising outcomes. Furthermore, new studies by our research group, suggests that bis-aryldiiminoacenaphthene ligands may also be effective, and even in- crease catalyst activity of such systems. However, such complexes regularly incorporate halo- gens as counterions. The impact of the diimine backbone on the catalytic activity and stability was investigated in the newly synthesised compounds. Additionally, the effects of the coun- terion and chelating solvent on the activity and stability were examined. Characterization of all compounds included mono and heteronuclear 1D and 2D-NMR, IR, EA, UV/Vis, and, when possible, X-ray diffraction. The efficiency of all compounds was tested in the oxidation reaction, and they all revealed to be active. Various conditions of the catalytic system were studied to optimize it, and subsequently, the catalytic system was tested with benzyl, allylic, and aliphatic alcohols for efficiency.
publishDate 2023
dc.date.none.fl_str_mv 2023-11
2023-11-01T00:00:00Z
2024-01-31T12:25:58Z
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
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instacron:RCAAP
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